CN105102587B - Converting-plastics are alkene and aromatic products - Google Patents

Converting-plastics are alkene and aromatic products Download PDF

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Publication number
CN105102587B
CN105102587B CN201380075524.0A CN201380075524A CN105102587B CN 105102587 B CN105102587 B CN 105102587B CN 201380075524 A CN201380075524 A CN 201380075524A CN 105102587 B CN105102587 B CN 105102587B
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catalyst
zsm
zeolite
catalytic cracking
carbon monoxide
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CN105102587A (en
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拉维钱德·纳拉亚纳斯瓦米
克里希纳·库马尔·拉马穆尔蒂
普斯·斯里尼瓦桑
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Saudi Basic Industries Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J2029/062—Mixtures of different aluminosilicates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Processing Of Solid Wastes (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

The carbon monoxide-olefin polymeric for producing alkene and aromatic compounds from raw material is formed by fluid catalytic cracking (FCC) catalyst and the zeolite catalysts of ZSM 5, wherein, by the gross weight meter of the FCC catalyst and the zeolite catalysts of the ZSM 5, the amount of the zeolite catalysts of ZSM 5 accounts for 10wt.% or more.The carbon monoxide-olefin polymeric can be used for by the way that hydrocarbon feed and the carbon monoxide-olefin polymeric are introduced into reactor, and at least a portion of the reactor is under 550 DEG C or higher of temperature of reactor, produced from raw material in the method for alkene and aromatic compounds.The raw material and carbon monoxide-olefin polymeric are introduced into the reactor with 6 or bigger catalyst and charging (C/F) ratio.

Description

Converting-plastics are alkene and aromatic products
Technical field
The present invention relates to be alkene and aromatic compounds by being pyrolyzed converting-plastics.
Background technology
Waste plastics is largely transferred into landfill or is incinerated, and wherein smaller portions, which are transferred into, recycles.In these years, with The increase of regulation and the taxation to landfill, post consumer waste be recycled or burn for energy regenerating percentage just by It is cumulative to add.The Plastics Europe statistics of 2009 shows, about 24.4 million tons of waste plastics is produced in Europe.Its In, handle 54% by recycling (22.6%) or energy regenerating (31.3%).It is about that plastics are transferred into landfill 46.1%.Therefore, waste plastics is manipulated so into landfill is just becoming more and more difficult.
It can be classified according to the classification that the feedstock circulation of waste plastics utilizes for producing product such as naphtha, ethene, third The pyrolysis of alkene and the waste plastics of aromatic compounds.As naphtha price significantly improves, with entering to less expensive gaseous state hydrocarbon charging The steam cracking device of row operation is compared, and the steam cracking device operated to naphtha feed is in unfavorable status.Such as Fruit equivalent comes from converting-plastics process, and a part of naphtha that such as product of pyrolysis is replaced into steam cracking device enters Material, the then economic situation of the steam cracking device operated to naphtha feed will improve.
In order to influence the economic situation of continuous larger numbers of steam cracking device factory operation, it is necessary that be pyrolyzed Journey is also continuous.Such large-scale plant is not present today, waste plastics is directly translated into oil by it in one step Chemical products.Previous trial all over the world is absorbed in from waste plastics always generates liquid fuel.These factories be scale compared with Small or characteristic is modular.The reaction carried out in such small-scale factory also carries out the longer residence time, from And the continuous operation that they are poorly suitable on more extensive.The trial of some early stages is also focused on to generate from waste plastics and used In the raw material of steam cracking device.However, these depend on the successful availability of steam cracking furnace.In addition, in pyrolysis furnace this The conversion of steam cracking device charging generally will result in the methane of higher amount caused by a little, and it is undesirable.
Therefore, it is necessary to for plastics to be directly translated into petrochemical industry product, such as alkene and the method for aromatic compounds, its The formation of methane is reduced to greatest extent, and it maximizes alkene and the yield of aromatic compounds.
The content of the invention
Carry out producing alkene and aromatic compounds by raw material by introducing hydrocarbon feed and carbon monoxide-olefin polymeric in reactor The method of thing, at least one of reactor are under 550C or higher temperature of reactor.Carbon monoxide-olefin polymeric is that fluidisation is urged Change cracking (FCC) catalyst and ZSM-5 zeolite catalyst, the amount of wherein ZSM-5 zeolite catalyst account for FCC catalyst and ZSM-5 10wt.% of gross weight of zeolite catalyst or more.With 6 or bigger catalyst and charge ratio by raw material and catalyst combination Thing introduces reactor.Allow at least one at least one of raw material is converted into alkene and aromatic compounds in reactor Kind.The product stream stock for including at least one of the alkene and aromatic compounds is removed from reactor.
In some embodiments, FCC catalyst includes following at least one：X-type zeolite, y-type zeolite, USY boilings Stone, modenite, faujasite, nano-crystalline zeolites, MCM mesopore materials, SBA-15, silicon-aluminate or phosphate (silico- Alumino phosphate), phosphoric acid gallium and titanium phosphate.
FCC catalyst can also be embedded at least one of Y zeolites and USY zeolite in matrix, FCC catalyst With 100m2/ g to 400m2/ g total surface area, by weight 0 to 0.5% coke laydown amount.
In some applications, FCC catalyst is with the non-fresh of the coke laydown by weight more than 0 to 0.5% FCC catalyst.In some embodiments, FCC catalyst can have 100m2/ g to 200m2/ g total surface area.
In some embodiments, the amount of the ZSM-5 zeolite catalyst of carbon monoxide-olefin polymeric accounts for FCC catalyst and ZSM-5 The 10wt.% of the gross weight of zeolite catalyst to 50wt.%.In other embodiments, the ZSM-5 zeolite of carbon monoxide-olefin polymeric The amount of catalyst accounts for the 30wt.% to 45wt.% of the gross weight of FCC catalyst and ZSM-5 zeolite catalyst.
In some cases, reactor can be operated, wherein at least one of reactor is at 570 DEG C to 730 DEG C temperature of reactor under.In some embodiments, reactor can be following at least one：Fluidized-bed reactor, bubbling Bed reactor, slurry-phase reactor, reacting in rotary kiln device and packed bed reactor.
In some applications, raw material and carbon monoxide-olefin polymeric can be introduced instead with charge ratio with 8 or bigger catalyst Answer device.Raw material can be following at least one：Polyolefin, polyethylene, polypropylene, polystyrene, PET (PET), polyvinyl chloride (PVC), polyamide, makrolon, polyurethane, polyester, natural and synthetic rubber, tire, filling polymerization Thing, composite, plastic alloy, plastics, biomass, bio oil and the oil of dissolving in a solvent.
In another aspect of the present invention, there is provided for producing the catalyst group of alkene and aromatic compounds from hydrocarbon feed Compound.Carbon monoxide-olefin polymeric includes the mixture of fluid catalytic cracking (FCC) catalyst and ZSM-5 zeolite catalyst, wherein The amount of ZSM-5 zeolite catalyst accounts for the 10wt.% to 50wt.% of the gross weight of FCC catalyst and ZSM-5 zeolite catalyst.
In some more specifically embodiments, the amount of the ZSM-5 zeolite catalyst of carbon monoxide-olefin polymeric accounts for FCC catalyst With the 30wt.% to 45wt.% of the gross weight of ZSM-5 zeolite catalyst.
In some applications, FCC catalyst can be embedded at least one in Y zeolites and the USY zeolite in matrix Kind, FCC catalyst has 100m2/ g to 400m2/ g total surface area, by weight 0 to 0.5% coke laydown amount.Other In, FCC catalyst includes following at least one：X-type zeolite, y-type zeolite, USY zeolite, modenite, faujasite, receive Rice crystalline zeolites, MCM mesopore materials, SBA-15, silicoaluminophosphate, phosphoric acid gallium and titanium phosphate.
FCC catalyst can be the non-fresh FCC catalyst with the coke laydown by weight more than 0 to 0.5%. In some cases, non-fresh FCC catalyst can have 100 to 200m2/ g total surface area.
In some embodiments, FCC catalyst is embedded at least one in Y zeolites and the USY zeolite in matrix Kind, FCC catalyst has 100m2/ g to 400m2/ g total surface area.In some cases, such FCC catalyst can be Non-fresh catalyst with the coke laydown for being more than 0 to 0.5% by weight.In some embodiments, such FCC Catalyst can further have 100m2/ g to 200m2/ g total surface area.
In some applications, FCC catalyst includes at least one of Y zeolites and USY zeolite, Y zeolites and the USY boiling At least one of stone and ZSM-5 zeolite catalyst are each embedded in same matrix.
Brief description of the drawings
For a more complete understanding of the present invention, now come together together with accompanying drawing with reference to following description, wherein：
Fig. 1 is light gaseous olefin yield relative to the converting middle carbon monoxide-olefin polymeric used in plastic raw materials The curve map of ZSM-5 zeolite catalyst content；
Fig. 2 is that light gaseous olefin yield turns relative to the pyrolysis of the plastic raw materials in the carbon monoxide-olefin polymeric using the present invention The curve map of temperature of reactor in change；
Fig. 3 is different light gaseous olefin yields relative to the converting middle catalyst combination used in plastic raw materials The curve map of the ZSM-5 zeolite catalyst content of thing；
Fig. 4 is different light gaseous olefin yields relative to the plastic raw materials in the carbon monoxide-olefin polymeric using the present invention The curve map of temperature of reactor in converting；
Fig. 5 is methane and ethylene yield relative to the converting middle carbon monoxide-olefin polymeric used in plastic raw materials The curve map of ZSM-5 zeolite catalyst content；
Fig. 6 is that methane and ethylene yield turn relative to the pyrolysis of the plastic raw materials in the carbon monoxide-olefin polymeric using the present invention The curve map of temperature of reactor in change；
Fig. 7 is weight liquid product yield relative to the converting middle carbon monoxide-olefin polymeric used in plastic raw materials The curve map of ZSM-5 zeolite catalyst content；
Fig. 8 is that weight liquid product yield turns relative to the pyrolysis of the plastic raw materials in the carbon monoxide-olefin polymeric using the present invention The curve map of temperature of reactor in change；
Fig. 9 is aromatics yield relative to the converting middle carbon monoxide-olefin polymeric used in plastic raw materials The curve map of ZSM-5 zeolite catalyst content；
Figure 10 is pyrolysis of the aromatics yield relative to the plastic raw materials in the carbon monoxide-olefin polymeric using the present invention The curve map of temperature of reactor in conversion；
Figure 11 is that coke yield is boiled relative to the ZSM-5 of the converting middle carbon monoxide-olefin polymeric used in plastic raw materials The curve map of stone catalyst content；And
Figure 12 is that coke yield turns relative to the pyrolysis in the plastic raw materials using carbon monoxide-olefin polymeric as disclosed herein The curve map of temperature of reactor in change.
Embodiment
As described herein, plastics and other hydrocarbon are changed into monomer by being pyrolyzed, it has high light gaseous olefin (for example, ethene, propylene and butylene) and aromatics yield, and there is low methane production.Can be in the low residence time The conversion is completed in the case of (order of magnitude of second), so that it is highly suitable for large-scale commercial applications operation.
This method uses fluid catalytic cracking (FCC) catalyst and ZSM-5 zeolite catalyst additive, its use that is bonded to each other In carbon monoxide-olefin polymeric to promote the converting of plastics or hydrocarbon charging.FCC catalyst is those catalyst, and it is used for oil original The cracking of material.Such petroleum can include the vacuum gas oil (vacuum from crude oil atmospheric and vacuum distillation plant Gas oil) (350-550 DEG C of boiling range), AGO (atmospheric gas oil) (atmospheric gas oil) and diesel oil (220-370 DEG C of boiling range), Naphtha (<35 DEG C to 220 DEG C of boiling range) or residue (>550 DEG C of boiling ranges), or produced in refinery by all secondary operation Various such stream stocks, including hydrotreating, hydrogenation cracking, coking, visbreaking (visbreaking), solvent deasphalting, Fluid catalytic cracking, naphtha reforming and this or their variant.FCC catalyst is generally by large pore molecular sieve or zeolite group Into.Large pore zeolite is those zeolites, and it hasOr bigger average pore size, more generallyTo aboutFor FCC The suitable large pore zeolite of catalyst can include X-type and y-type zeolite, modenite and faujasite, nano-crystalline zeolites, MCM mesopore materials (MCM-41, MCM-48, MCM-50 and other mesopore materials), SBA-15 and silicon-aluminate or phosphate, phosphoric acid gallium, with And titanium phosphate.It is especially useful that y-type zeolite.
In the y-type zeolite for FCC catalyst, silica and alumina tetrahedra are connected by oxygen key.In order to Heat and hydrothermal stability are assigned, Y zeolites can be handled to knock out some framework aluminum oxide (framework alumina) (one of these approach are steam processing at high temperature).Generally, Y zeolites have about 2.5:1 Si/Al ratio.The Y zeolites of dealuminzation lead to Often with having 4:1 or bigger Si/Al ratio.The Y zeolites of dealuminzation with higher framework Si/Al ratio are with stronger acid sites (site) (acid sites of separation) and be heat and hydro-thermal it is more stable, therefore be referred to as overstable Y zeolites (USY boil Stone).In device such as fluid catalytic cracking, wherein catalyst sees 700 DEG C of temperature and moisture in catalyst regenerator, heat It is important with hydrothermal stability, so that catalyst activity is kept the long period.Therefore, the USY in such operation Zeolite can be preferable FCC catalyst.
Can be with the overstable zeolite of rare earth exchanged.Based on the weight of zeolite, content of rare earth can be higher than 0% and can be with Up to 10%, wherein the 0.1-3% based on the weight of zeolite is typical.However, content of rare earth is higher, by being advantageous to hydrogen migration Reaction loses more Product olefins degree (olefinicity) to prepare paraffin.A certain amount of rare earth can be had in zeolite Y , because it assigns zeolite stability.Rare earth material can include cerium, lanthanum and other rare earth materials.
It is it should be appreciated that useful, suitable on listing or being described as in the content of the invention and embodiment Deng any concentration or amount scope, it is intended to including the every kind of concentration or amount in the range of this, including end points, and be considered as Through what is clearly stated.For example, " 1 to 10 scope " should be interpreted that expression along the continuous collection from about 1 to about 10 (continuum) each and all possible numeral.Therefore, even if particular data point within the range or in the model It is explicitly indicated or refers to even without data point in enclosing and be only specific several, it should be understood that present inventors appreciated that and reason Any and all data point of solution within the range be considered as it has already been indicated that and the present inventor possess gamut and at this In the range of institute a little.
FCC catalyst is typically the above-mentioned zeolite being embedded in active matrix.Matrix can be formed from active material, such as living Property alumina material, it can be noncrystal or crystal, adhesive material, such as aluminum oxide or silica and inert filler, Such as kaolin.The zeolite component being embedded in the matrix of FCC catalyst can account for 10 to 90% based on the weight of FCC catalyst. The FCC catalyst with the zeolitic material being embedded in active matrix material can be formed by being spray dried to microballoon.This A little catalyst be it is hard and with extraordinary abrasion performance with bear the pellet-pellet that generally occurs when fluidized catalyst with And the collision of particle-wall.The particle diameter distribution of FCC catalyst can be more than 0 to 150 micron.In some embodiments, 90- 95% particle diameter distribution can be in the range of more than 0 to 110 micron or 120 microns, and 5-10% particle have be more than 110 microns of particle diameter.Due to particle diameter distribution, the average or median particle diameter of FCC catalyst is typically 70 to 75 microns.In some feelings Under condition, the relatively fine particle of FCC catalyst can be used together with larger particles for providing good fluidisation.In some implementations In mode, for example, 15% or less FCC catalyst can have 40 microns or smaller of particle diameter.By in fine grained and slightly The presence of particulate (fine) assigns good fluidisation in the mixture of particle.Fine grain forfeiture causes the separation of flow.
FCC catalyst can be further characterized based on some physics, chemistry, surface characteristic and catalytic activity.Fresh FCC Catalyst has very high surface area, usually 300-400m2/ g or higher, and high activity.Because fresh FCC is catalyzed The high activity of agent, the high yield of coke, such as 8-10wt.% are typically resulted in using the cracking of the petroleum of fresh FCC catalyst, And light gas.When required for all heats generated by coke formation can not be cracking, coke it is very high Yield can influence the thermal balance of reaction.Therefore, it is probably necessary to remove heat from reactor-regenerator system.This meaning , do not utilize charging effectively.If producing the coke required for just enough support cracking process heat demands, can have more Have an economic value, wherein surplus (otherwise being formed into excess coke) be used for formed with product.In addition, come from fresh FCC The high yield of the light gas (methane, ethane) of catalyst is undesirable and can exceed factory's humid gas compressor apparatus Limitation or the limitation of FCC compounds.The high yield of methane is undesirable, and this is due to that it is limited in terms of chemicals is formed Effectiveness (even if higher hydrocarbon can be formed by methane by synthesis gas-methanol-to-olefins path).On the other hand, ethane can be used In preparing ethene, a kind of valuable chemicals.However, in most cases, higher ethane yields are along with higher Methane production.
In order to overcome these problems, generally FCC cracking units are operated by maintaining constant active or conversion ratio.This is logical The partial inactivation catalyst of circulation storage is crossed, the used or non-fresh catalyst of fraction is then periodically removed, is used in combination Fresh FCC catalyst is supplied, to complete.The use of used or non-fresh catalyst helps to maintain catalyst activity to exist Constant is horizontal without producing high-caliber methane and coke.Under plant operating conditions, the circulation storage of factory's catalyst It is partial inactivation or balance.The partial catalyst periodically cleared out of is dead catalyst.Therefore, fresh catalyst is supplemented in addition Before agent, for catalyst activity, in FCC apparatus, it generally has the identical activity of recycling catalyst storage.Generally exist Catalyst make-up and removing are periodically carried out in the FCC apparatus of operation.Recycling catalyst storage has fresh catalyst substantially 50% or less surface area, and the activity of substantially 10 conversion units of the activity with less than fresh catalyst or conversion ratio Or conversion ratio.In other words, if fresh catalyst will provide 80wt.% vacuum gas oil (vacuum gas oil) scope Material is to dry gas (dry gas) (H2-C2)、LPG(C3-C4), the conversion ratio of gasoline (35-220 DEG C of boiling point hydrocarbon) and coke, that Cyclic part decaying catalyst storage can provide 70wt.% conversion ratio.The FCC that EGR is added by supplementing is fresh Catalyst granules, before it is removed out, a couple of days (aging) will be averagely spent in a device.Therefore, because catalyst is deposited Amount is carried out the fact that daily iron supplement, the catalyst granules that recycling catalyst storage will generally have different agings, i.e. in storage The age distribution of catalyst granules be present.The catalyst activity of particle is proportional to its inactivation in FCC apparatus, itself and then It is proportional to the aging of catalyst.Table 1 below is listed in the fresh typical characteristics between spent FCC catalyst.
Table 1
* it is typically 10-15wt.% that Sox and S, which reduces additive (reduction additive),.Sox and S reduces addition Agent is by without the catalyst activity for cracking, thus by dilute catalyst activity.These additives are generally added to meet For being produced from the stream stock of FCC apparatus and the motor vehicle fuel code requirement of environment being discharged into for slowing down Sox.Generally, magnesium Oxide be used for such additive and they for fracture molecule by with relatively low or without conversion ratio and thus will Reduce the ability that FCC catalyst changes into heavier molecule lighter molecule, i.e. activity dilution.
The present invention can utilize fresh FCC catalyst, non-fresh FCC catalyst, or both mixture.This can be wrapped Spent FCC catalyst is included, it is (as described earlier) removed from fluid catalytic cracking process.Because spent FCC catalyst leads to It is often the waste from fluid catalytic cracking process, so it is special that it, which is used to plastics and other hydrocarbon changing into useful product, Favourable.This is due to its lower cost and availability and does not form the favourable of more coke and methane due to it Activity.Spent FCC catalyst is substantially " used " or " non-fresh " FCC catalyst, and it has been used for fluid catalytic cracking Journey and it has been removed to be changed (as described earlier) with fresh catalyst.As used in this article, on FCC catalyst, statement " non-fresh " are intended to any FCC catalyst (as they have been described), and it has a certain amount of (i.e. more than 0%) coke laydown.Fresh FCC catalyst will not have coke laydown.In some embodiments, by catalyst Weight meter, the coke laydown on non-fresh FCC catalyst can be 0.01%, 0.05%, 0.1%, 0.2%, 0.3%th, 0.4% or more.Generally, based on the weight of catalyst, the coke laydown of non-fresh FCC catalyst will be greater than 0 To 0.5%.Spent FCC catalyst, which can have, possesses the coking non-fresh catalyst granules of different degrees of catalyst, and this is Due to the difference of catalyst aging used in cracking process.Compared with fresh FCC catalyst, non-fresh FCC catalysis Agent also has reduced surface area, and this is due to the catalyst hydrothermal deactivation in FCC apparatus.The typical case of non-fresh catalyst Surface area can be 100m2/ g to 200m2/g.In addition, in some embodiments, FCC catalyst can include non-fresh Or spent FCC catalyst and fresh FCC catalyst combination and can be used for converting reaction.
The ZSM-5 zeolite catalyst additive being used together with FCC catalyst is molecular sieve, and it is comprising intersecting two dimension The porous material of pore structure (there are 10 membered oxygen rings).During zeolitic material with above-mentioned 10 oxygen ring hole structure is often classified as Hole zeolite.Such mesopore zeolite generally hasExtremelyBore dia.ZSM-5 zeolite is intermediate pore size boiling Stone, its bore dia are about 5.1 to aboutZSM-5 zeolite and their preparation are described in U.S. Patent number 3, and 702,886, It is incorporated into herein by reference.ZSM-5 zeolite can be free from any Metal Supported.
ZSM-5 zeolite is also typically embedded in active matrix, and it can be with those matrix of the zeolite for FCC catalyst (as described earlier) is same or like.Matrix can be formed from active material, such as activated alumina material, adhesive material Material, such as aluminum oxide or silica, and inert filler, such as kaolin.
Based on the weight of ZSM-5 zeolite catalyst, the zeolite component being embedded in the matrix of ZSM-5 catalyst can account for 5 To 90%, more typically 10 to 80% based on the weight of ZSM-5 zeolite catalyst, and even more typically urged by ZSM-5 zeolite The weight meter 10 to 50% of agent.It can also be embedded in by being spray dried to microballoon to be formed to have in active matrix material The ZSM-5 zeolite catalyst of ZSM-5 zeolite material.The particle diameter distribution of ZSM-5 zeolite catalyst can be more than 0 to 150 micron. In some embodiments, 90-95% particle diameter distribution can be in the range of more than 0 to 110 micron or 120 microns. The average or median particle diameter of ZSM-5 zeolite catalyst is typically 70 to 75 microns.In some cases, can be together with larger particles The relatively fine particle of ZSM-5 zeolite catalyst is used together to provide good fluidisation.In some embodiments, for example, 15% Or less ZSM-5 zeolite catalyst can have 40 microns or smaller of particle diameter.
In some embodiments, the zeolitic material of FCC catalyst and ZSM-5 zeolite (such as X-type zeolite or y-type zeolite) It can embed and be formed in identical matrix material unit, so as to be formed comprising FCC catalyst and ZSM-5 catalyst materials Catalyst granules.These particles can have with being previously directed to described by single FCC catalyst and ZSM-5 zeolite catalyst Those identical sizes and construction (configuration).FCC and ZSM-5 zeolite composition are combined in single-matrix or particle The advantages of one of be, it can cause greater activity, and this can be non-live by being reduced to greatest extent in independent catalyst Property diluent obtains.
For particle diameter distribution and abrasion performance, select to have and FCC catalyst for the catalyst of plastics pyrolysis Similar characteristic, because these parameters can significantly influence the integrality of catalyst formulation in operating fluidized bed environment. Very thin particle can cause their high loss, and this is due to them by product gas entrained with, and larger catalyst Particle diameter tends not to suitably fluidize and cause activity heterogeneous.However, in some embodiments, catalyst has wherein In the system that less possibility is lost, such as in rotary kiln and slurry-phase reactor, FCC catalyst and ZSM-5 can be used The pure form of zeolite is without any host material or compared with small particle.
In the present invention, the valuable of light gaseous olefin and aromatic compounds is produced using the plastics pyrolysis of antigravity system Monomer, such as benzene, toluene and dimethylbenzene.By using the combination of antigravity system and process conditions, process can be produced Alkene and the desired yield of aromatic compounds are arrived in rate regulation.Have found, use FCC catalyst and ZSM-5 zeolite catalyst The combination (as has been described) of additive, compared with using only FCC catalyst, the alkene and virtue of higher yields can be obtained Compounds of group.Specifically, the 10wt.% of gross weight comprising FCC catalyst and ZSM-5 zeolite catalyst or more ZSM-5 The antigravity system of zeolite catalyst provides the alkene and aromatic compounds of increase yield.As used in this article, ZSM-5 The percentage by weight of zeolite catalyst and FCC catalyst is the gross weight based on catalyst, including any host material is (unless another Clearly state).In the case of not using host material in the reaction, the weight of ZSM-5 zeolite catalyst and FCC catalyst Percentage is only the percentage by weight of zeolite.
In some embodiments, the amount of the ZSM-5 zeolite catalyst of carbon monoxide-olefin polymeric accounts for FCC catalyst and ZSM-5 The 10wt.% of the gross weight of zeolite catalyst to 50wt.%.Therefore, the amount of the ZSM-5 zeolite catalyst of carbon monoxide-olefin polymeric accounts for 10wt.%, 15%wt.% of the gross weight of FCC catalyst and ZSM-5 zeolite catalyst, 20%wt.%, 25%wt.%, 30%wt.% or 35%wt.% is to 40%wt.%, 45%wt.% or 50wt.%.In other embodiments, catalyst The amount of the ZSM-5 zeolite catalyst of composition accounts for the 30wt.% of the gross weight of FCC catalyst and ZSM-5 zeolite catalyst extremely 45wt.%.In further embodiment, the amount of the ZSM-5 zeolite catalyst of carbon monoxide-olefin polymeric account for FCC catalyst and The 35wt.% of the gross weight of ZSM-5 zeolite catalyst to 40wt.%.Under specific circumstances, it was found that when by FCC catalyst and The gross weight meter of ZSM-5 zeolite catalyst, when the dosage of ZSM-5 zeolite catalyst is about 37.5wt.%, produce maximum output Alkene and aromatic compounds.
The plastics charging used in conversion reaction can consist essentially of all plastic materials, such as by organic polymer Those formed.Non-limiting examples include polyolefin, such as polyethylene, polypropylene, polystyrene, poly terephthalic acid second two Ester (PET), polyvinyl chloride (PVC), polyamide, makrolon, polyurethane, polyester, natural and synthetic rubber, tire, filling are poly- Compound, composite and plastic alloy, the plastics of dissolving in a solvent etc..Although plastics charging can be used for conversion reaction, Other hydrocarbon materials are also used as raw material.These hydrocarbon can include biomass, bio oil, oil etc..Therefore, although the present invention is main The conversion of plastics charging is directed to, but it is to be understood that, it is suitable for and covering the uses of other hydrocarbon.When expectation is given birth to When producing light gaseous olefin, the plastics of polyolefin charging or mainly or the charging of the plastics comprising considerable fraction of polyolefin can be with It is preferable.The mixture (without limitation) of a variety of plastics and hydrocarbon material can be used.
It can be fed with many different forms to provide plastics.In small-scale operation, plastics charging can be powder The form at end.In fairly large operation, plastics charging can be the form of pellet, as having 1 to 5mm particle diameters.
Catalyst and plastics charging can be mixed or can individually fed before reactor is introduced.For The amount or ratio of the catalyst of plastics charging can change and can depend on the particular system and the treatment conditions that use.Can To convert plastics with charging (C/F) ratio using very low or very high catalyst.It can be needed in the case of low C/F ratios Longer time of contact, and for high C/F ratios, then it can need shorter time of contact.In testing, using 4 to 12 C/F Than wherein 6 to 9 C/F ratios are most frequently used.(recirculating fluidized bed can be wherein used in large-scale industrial process Stalk (riser) or downspout (downer)), C/F ratios can be determined by reactor thermal balance or other parameters.
Various reactors can be used for conversion process.For large-scale operation, can use recirculating fluidized bed stalk or Descending liquid pipe reactor.The bubbling bed reactor of its situ bubbling catalyst can also be used, charging is added into bubbling bed.One In a little applications, slurry type of reactor and rotary kiln type of reactor can also be used.
The charging of the carbon monoxide-olefin polymeric and plastics that are made up of FCC catalyst and ZSM-5 zeolite catalyst is introduced into (mixing Ground individually adds) reactor, such as fluidized-bed reactor (as described earlier).Reaction is operated under temperature of reactor Device, wherein all or part of reactor is at 550 DEG C or higher of temperature.In some embodiments, in reactor At a temperature of operate reactor, wherein all or part of reactor is at 570 DEG C or higher of temperature.In some embodiment party In formula, reactor is operated under temperature of reactor, wherein all or part of reactor is the temperature at 550 DEG C to 730 DEG C Under, more particularly 570 DEG C to 680 DEG C, 690 DEG C to 700 DEG C.Reactor pressure can be environmental pressure to 50 bars (g) (5MPa) And more typically environmental pressure is to 3 bars (g) (0.3MPa).Nitrogen, dry gas (dry gas) (H2-C2), steam or other inertia The mixture of gas or gas may be used as carrier gas, wherein entrained catalyst and charging.The scope of fluidizing gas flow rate can be with Different mode uses, such as bubbling fluidized bed pattern, recirculating fluidized bed pattern, slurry tank reactor pattern.It can also use other Reactor configuration (configuration) and pattern.In certain embodiments, ciculation fluidized pattern can be used, because it There is provided and preferably conduct heat and contact the coke management aspect the advantages of, between charging and catalyst.Catalyst/charge ratio (C/ F can be) as little as 2 up to 30 and more typical in the range of 4-12.
It is converting to light gaseous olefin and aromatic compounds that plastics can fairly quickly occur, i.e., at several seconds It is interior.Caused thermal decomposition product includes light gaseous olefin, such as ethene, propylene, butylene, and aromatic compounds, as benzene, toluene, Dimethylbenzene and ethylo benzene.These materials can be optionally produced in large quantities.Generation charging plastics are fully converted into various productions Thing.Caused product includes gas (H2-C4), it is gasoline or naphtha (35-220 DEG C of boiling point), diesel oil (220-370 DEG C of boiling point), small Partial relatively density current stock (boiling point>370 DEG C) and coke.Can be by using different catalyst formulation or any or all of Above-mentioned parameter (include the specific features of time of contact, fluidized flow speed and reactor hardware, as diameter, length or charging and/ Or gas distribution design or the related hardware modifications of mixing/contact, product be re-circulated into reactor be used for further conversion with And such other parameters) change the yield of various products.Saturated products are also produced, such as methane, ethane, propane and butane, And hydrogen (H2).In testing, the methane and butadiene (difference of low-yield are obtained<2wt.% and 0.5wt.%).This shows, Even if use temperature severity (temperature severity) it is higher (i.e. 550 DEG C or higher), it was observed that activity lead It is probably due to the catalytic activity of non-thermal cracking.Successfully suppressing methanogenesis and high conversion is provided simultaneously and minimized Carbon monoxide-olefin polymeric can be used under conditions of weight product.The process also minimizes the formation of weight product liquid, i.e. those boiling points Product heavy ends (heavy end) higher than 370 DEG C.
Caused thermal decomposition product can be used for various processes.Such as formation light gaseous olefin (ethene, propylene, And butylene) can be used for polymerizeing, aromatic compounds may be used as the construction unit of derivative or can be used for application-specific in itself, Saturated gas can further be cracked into light gaseous olefin or can be directed to fuel gas (H2-C2) and LPG (C3-C4) pond or can For use as pyrolysis or it is any other during fuel.It is necessary to be provided for pyrolytic process that the coke of formation may be used as the energy Heat demand.
Generally speaking, the method for alkene and aromatic compounds is produced from raw material to be included：In the reactor introduce hydrocarbon feed and Carbon monoxide-olefin polymeric, at least one of reactor are that carbon monoxide-olefin polymeric includes under 550 DEG C or higher of temperature of reactor Fluid catalytic cracking (FCC) catalyst and ZSM-5 zeolite catalyst, the amount of wherein ZSM-5 zeolite catalyst account for FCC catalyst and At least 10wt.% of the gross weight of ZSM-5 zeolite catalyst, with 6 or bigger catalyst and charge ratio by raw material and catalyst Composition introduces reactor；At least one of raw material is allowed to be converted into alkene and aromatic compounds at least in reactor It is a kind of；And the product stream stock for including at least one of the alkene and aromatic compounds is removed from reactor.In above-mentioned side In method, apply at least one of following condition：FCC catalyst is made up of following at least one：X-type zeolite, y-type zeolite, USY boilings Stone, modenite, faujasite, nano-crystalline zeolites, MCM mesopore materials, SBA-15, silicon-aluminate or phosphate, phosphoric acid gallium and phosphorus Sour titanium, more preferably wherein FCC catalyst is made up of at least one of the Y zeolites being embedded in matrix and USY zeolite, FCC Catalyst has 100m2/ g to 400m2/ g total surface area, by weight, coke laydown amount are 0 to 0.5%；FCC catalyst is Non-fresh FCC catalyst, it is with the coke laydown more than 0 to 0.5% by weight；FCC catalyst has 100m2/ g is extremely 200m2/ g total surface area；The amount of the ZSM-5 zeolite catalyst of carbon monoxide-olefin polymeric accounts for FCC catalyst and ZSM-5 zeolite catalysis The 10wt.% of the gross weight of agent to 50wt.%；The amount of the ZSM-5 zeolite catalyst of carbon monoxide-olefin polymeric account for FCC catalyst and The 30wt.% of the gross weight of ZSM-5 zeolite catalyst to 45wt.%；At least one of reactor be at 570 DEG C extremely Under 730 DEG C of temperature of reactor；With 8 or bigger catalyst and charge ratio, raw material and carbon monoxide-olefin polymeric are introduced into reactor； Raw material includes following at least one：It is polyolefin, polyethylene, polypropylene, polystyrene, PET (PET), poly- Vinyl chloride (PVC), polyamide, makrolon, polyurethane, polyester, natural and synthetic rubber, tire, filled polymer, composite wood Material, plastic alloy, plastics, biomass, bio oil and the oil of dissolving in a solvent；And reactor be fluidized-bed reactor, At least one of bubbling bed reactor, slurry-phase reactor, reacting in rotary kiln device and packed bed reactor.
In any aforementioned embodiments, for producing alkene and the carbon monoxide-olefin polymeric bag of aromatic compounds from hydrocarbon feed Mixture containing fluid catalytic cracking (FCC) catalyst and ZSM-5 zeolite catalyst, the amount of wherein ZSM-5 zeolite catalyst account for The 10wt.% of the gross weight of FCC catalyst and ZSM-5 zeolite catalyst to 50wt.%, preferably wherein carbon monoxide-olefin polymeric The amount of ZSM-5 zeolite catalyst accounts for the 30wt.% to 45wt.% of the gross weight of FCC catalyst and ZSM-5 zeolite catalyst, more Preferably wherein FCC catalyst is made up of at least one of the Y zeolites being embedded in matrix and USY zeolite, FCC catalyst tool There is 100m2/ g to 400m2/ g total surface area, by weight, coke laydown amount are 0 to 0.5%；And wherein meet following bar At least one of part：FCC catalyst is made up of following at least one：X-type zeolite, y-type zeolite, USY zeolite, modenite, eight Face zeolite, nano-crystalline zeolites, MCM mesopore materials, SBA-15, silicon-aluminate or phosphate (silico-alumino phosphate), Phosphoric acid gallium and titanium phosphate；FCC catalyst is non-fresh FCC catalyst, and by weight, it has Jiao more than 0 to 0.5% Carbon deposit, non-fresh FCC catalyst preferably have 100 to 200m2/ g total surface area；FCC catalyst is by being embedded in matrix In Y zeolites and at least one of USY zeolite composition, FCC catalyst preferably there is 100m2/ g to 400m2/ g total surface Product；FCC catalyst is non-fresh catalyst, and by weight, it has the coke laydown more than 0 to 0.5%, preferably wherein FCC catalyst has 100m2/ g to 200m2/ g total surface area；And FCC catalyst by Y zeolites and USY zeolite at least At least one of one kind composition, described Y zeolites and USY zeolite and ZSM-5 zeolite catalyst are each embedded in identical base In body.
Following examples are used for further illustrating the present invention.
Embodiment
In each embodiment presented below, the fluid bed in situ that using length be 783mm and internal diameter is 15mm is tested Room tubular reactor (in-situ fluidized bed lab tubular reactor).Reactor is placed in cracking zone 3 In area's tube furnace (split-zone 3-zone tubular furnace), there is independent temperature control for each area.Often The size in individual area is 9.3 inches (236.2mm).The total heated length for the reactor being placed in stove is 591mm.In each area Reactor wall temperature is measured at center and for controlling the heating in each stove area.Reactor, which has conical lower portion and utilized, to be placed in Thermocouple sheath is interior and is placed in the thermocouple measurement reactor beds temperature in reactor at the top of conical lower portion.In addition, Reactor wall temperature is measured at conical lower portion to ensure that the bottom of reactor is hot.Reactor bottom is placed on furnace bottom The middle part in area, for reducing the influence and maintenance reaction device bottom of stove end cap (furnace end cap) heat loss to greatest extent Portion's wall temperature is in 20 DEG C of the inside bed tempertaure of measurement of difference.
Plastics charging is the form of 200 microns of plastic powders.FCC catalyst is the spent FCC catalyst for being obtained from operation refinery. The FCC dead catalyst used is in the residual coke thereon with 0.23wt%.The ZSM-5 zeolite catalyst used is commercially available ZSM-5 zeolite catalyst.By rotating come mixed plastic charging and catalyst in cup, then feed to reactor.
Collect the converted product for carrying out autoreactor and condense within the condenser.Collected in gas collection vessel uncooled Product simultaneously analyzes gas composition using refinery gas analyzer (M/s AC Analyticals B.V., Holland).Utilize simulation GC (M/s AC Analyticals B.V., Holland) is distilled to characterize the boiling point distribution of product liquid.In addition, analyzed using DHA Instrument (M/s AC Analyticals B.V., Holland) is analyzed (up to C13 hydrocarbon) to carry out detailed hydrocarbon.Using based on IR's CO and CO2Analyzer determines to deposit coke on a catalyst.Matter is determined by adding up to the yield of gas, liquid and coke Amount balance.Single products collection efficiency is determined and reports based on normalization product.
Embodiment 1
Using be ground to 200 micron-scales pure HDPE plastic feed and 75wt.% FCC dead catalyst and The carbon monoxide-olefin polymeric of 25wt.% ZSM5 zeolite catalysts is tested.The plastics charging used is 0.75g and used Dry catalyst weight is 4.5g.This corresponds to the C/F ratios of 5.98 (~6.0).Will charging and catalyst charge to reactor (such as It is upper described).Before charging, the bed tempertaure such as measured by inside reactor thermocouple is 650 DEG C.It is (normal in 200Ncc/min Cc/min the N under)2Gas flow is used as fluidisation and carrier gas.As a result it is listed in table 2.
Table 2
C/F ratios 6.0
Reaction temperature during beginning 650.0
Methane 1.24
%H2, C1, C4 yield 54.1
% liquid yields 44.2
% coke yields 1.7
C4=, wt% 16.3
C3=, wt% 19.8
C2=, wt% 6.3
Total olefin 42.4
This embodiment illustrates, using pure polyene hydrocarbon charging, in high temperature severity (high temperature Severity under), high gas yield is possible, the methane without producing high yield.
Embodiment 2-13 experiment
For embodiment 2-13, the plastics of the mixing formed using the mixture by polyolefin, polystyrene (PS) and PET Charging, it has the consisting of for being listed in table 3.In powder form using the plastics mixed and together with catalyst (as previously described) Feed together to reactor.Temperature of reactor when reaction starts is to be measured before charging and catalyst is added in reactor Those.Fluidize N2Gas flow is 175Ncc/min.
Table 3
Material Amount
HDPE 19wt.%
LDPE 21wt.%
PP 24wt.%
C4-LLDPE 12wt.%
C6-LLDPE 6wt.%
PS 11wt.%
PET 7wt.%
Embodiment 2
Come together to use spent FCC catalyst together with different amounts of ZSM-5 zeolite catalyst (0 to 100 percentage).Reacting Tested before starting under 670 DEG C of temperature of reactor of setting.Use 9 C/F ratios.Use 6.8g dry catalyst and 0.75g Plastics are fed to be tested.Total light gaseous olefin (that is, the C of measurement2To C4).As a result Fig. 1 and table 4 are shown in.Such as can from Fig. 1 Go out, when the amount of the ZSM-5 zeolite catalyst additive in catalyst mixture is about 37.5wt.%, then realize maximum output Light gaseous olefin.
Table 4
The ZSM-5 zeolite catalyst content in catalyst mixture Wt.% 0 25 37.5 50 100
C/F ratios g/g 9.1 9 9 9 8.9
Reaction temperature during beginning ℃ 670 670 670 670 670
The dry catalyst of charging g 6.8 6.77 6.76 6.75 6.7
The feed weight of transfer g 0.75 0.75 0.75 0.75 0.75
Total light gaseous olefin (C2+C3+C4) yield Wt.% 24.5 33.4 36.4 34.2 31.5
Embodiment 3
Tested to determine that the different C/F of the temperature of reactor different when reacting beginning and 6 and 9 compare light gas The influence of body olefins yield production.By using the spent FCC catalyst comprising 62.5wt.% and 37.5wt.% ZSM-5 zeolite Catalyst (with 9 C/F ratios) and 75wt.% spent FCC catalyst and 25wt.% ZSM-5 zeolite catalyst are (with 6 C/F Than) catalyst mixture carry out these experiments.When adding charging and catalyst, temperature of reactor declines and reached rapidly Minimum value, then go up to its initial value before starting the reaction.Most temperature is recovered to occur after reactor is added One minute in.As a result Fig. 2 and table 5 and 6 are shown in.As figure it is seen that light gaseous olefin yield increases with temperature Add, and or about 670 DEG C be issued to maximum.Compared with relatively low C/F ratios (table 6), the higher 9 C/F ratios (table 5) of use, Olefins yield increase.
Table 5
Table 6
Embodiment 4
Tested to be determined as spent FCC catalyst and different amounts of ZSM-5 zeolite catalyst (that is, 0 to 100%) The yield of the different alkene of the function of carbon monoxide-olefin polymeric.At a temperature of 670 DEG C (react start when) and 9 C/F ratios under Reacted.As a result Fig. 3 and table 7 are shown in.As can be seen in Figure 3, it is about in ZSM-5 zeolite catalyst content Productivity of propylene is highest under 37.5wt.%.
Table 7
Embodiment 5
Tested to determine influence of the initial temperature to the yield of different alkene.The amount of ZSM-5 zeolite catalyst is to urge The 37.5wt.% of agent mixture.The C/F ratios used are listed in table 8.As a result Fig. 4 and table 8 are shown in.As that can see in Fig. 4 Go out, at a temperature of about 670 DEG C, obtain maximum output.
Table 8
Embodiment 6
Under 670 DEG C of initial reaction temperature, the different amounts of ZSM-5 zeolite catalyst in carbon monoxide-olefin polymeric is used (0% to 100%) is tested.Use 9 C/F ratios.Then ethene and methane production are measured, is as a result shown in Fig. 5 and table 9. Such as in Fig. 5 and table 9 as can be seen that in the range of the ZSM-5 zeolite catalyst content for antigravity system, methane production There is no significant changes.By contrast, ethylene yield is increased significantly to 7wt.% from 2wt.%, and this shows the operating condition in use Under carbon monoxide-olefin polymeric, methane production is suppressed.
Table 9
The ZSM-5 zeolite catalyst content in catalyst mixture Wt.% 0 25 37.5 50 100
C/F ratios g/g 9.07 9.0 9.0 9.0 8.92
Reaction temperature during beginning ℃ 670 670 670 670 670
The dry catalyst of charging g 6.80 6.77 6.76 6.75 6.70
The feed weight of transfer g 0.75 0.75 0.75 0.75 0.75
Methane Wt.% 1.00 0.81 0.90 0.79 1.13
Ethene Wt.% 1.98 5.11 6.52 6.22 6.71
Embodiment 7
Tested to determine influence of the initial temperature to methane and the yield of ethene.Carbon monoxide-olefin polymeric is 62.5% Wt.% FCC catalyst and 37.5wt.% ZSM-5 zeolite catalyst, use 9 C/F charge ratios.As a result Fig. 6 and table are shown in 10.As in fig. 6 it can be seen that in the range of temperature, methane production changes from 0.4wt.% to 1.3wt.%, and ethene produces Rate then changes from 4.2wt.% to 6.7wt.%.Again, the yield of methane is relatively low, and this shows, carbon monoxide-olefin polymeric and place The combination of manage bar part can suppress methane production and increase ethylene yield.
Table 10
Embodiment 8
Tested to be determined as spent FCC catalyst and different amounts of ZSM-5 zeolite catalyst (that is, 0 to 100%) The yield of the heavy product liquid (that is, product liquid of the boiling point higher than 370 DEG C) of the function of carbon monoxide-olefin polymeric.In 670 DEG C of temperature Reacted under degree and 9 C/F ratios.As a result Fig. 7 and table 11 are shown in.As in figure 7 it is seen that 50wt.% ZSM-5 More than zeolite catalysis agent content, the catalyst activity for producing weight product liquid is not optimal.Make under higher than this scope With the ZSM-5 zeolite catalyst of higher amount, catalyst activity becomes to dilute.
Table 11
Embodiment 9
Tested to determine initial temperature counterweight product liquid (that is, product liquid of the boiling point higher than 370 DEG C) yield Influence.Carbon monoxide-olefin polymeric is about 75%wt.% FCC catalyst and 25wt.% ZSM-5 zeolite catalyst, uses 6 C/F charge ratios.As a result Fig. 8 and table 12 are shown in.As shown in figure 8, under about 670 DEG C of initial reaction temperature, weight product liquid is It is low-down, when the temperature increases, produce increasing weight product liquid.
Table 12
Embodiment 10
Tested to be determined as spent FCC catalyst and different amounts of ZSM-5 zeolite catalyst (that is, 0% to 100%) Carbon monoxide-olefin polymeric function aromatic compounds yield.It is determined that the product liquid to be seethed with excitement at a temperature of less than 240 DEG C In aromatic products content.Reacted at 670 DEG C of temperature and 6 C/F ratios.As a result Fig. 9 and table 13 are shown in.Such as Fig. 9 institutes Show, product liquid is rich in aromatic content, using about 25wt.% or higher ZSM-5 zeolite catalyst content, realizes The aromatic content of even more high in product liquid.
Table 13
Embodiment 11
Tested to determine initial temperature to aromatic compounds in the product liquid that seethes with excitement at a temperature of less than 240 DEG C The influence of content.Carbon monoxide-olefin polymeric is 62.5wt.% FCC catalyst and 37.5wt.% ZSM-5 zeolite catalyst, is made With 6 C/F charge ratios.As a result Figure 10 and table 14 are shown in.As can be seen that at 635 DEG C or higher of temperature, obtained in Fig. 10 Obtain the aromatic compounds of the higher amount in product liquid.
Table 14
Temperature, DEG C The dry catalyst of charging The feed weight of transfer Aromatic content
700 8.95 1.50 75.37
670 8.95 1.50 74.71
635 8.95 1.50 75.03
600 8.95 1.50 69.23
Embodiment 12
Tested to determine the coke yield based on carbon monoxide-olefin polymeric.The carbon monoxide-olefin polymeric used is that useless FCC is urged Agent and different amounts of ZSM-5 zeolite catalyst (0wt.% to 100wt.%).It is using 9 C/F ratios and temperature of reactor 670℃.As a result Figure 11 and table 15 are shown in.
Table 15
ZSM-5 zeolite catalyst content in catalyst mixture Wt.% 0 25 37.5 50 100
C/F ratios g/g 9.07 9.0 9.0 9.0 8.92
Reaction temperature during beginning ℃ 670 670 670 670 670
The dry catalyst of charging g 6.80 6.77 6.76 6.75 6.70
The feed weight of transfer g 0.75 0.75 0.75 0.75 0.75
Coke yield Wt.% 5.72 4.86 4.93 4.59 4.58
Embodiment 13
Tested the influence of temperature of reactor STRENGTH ON COKE yield during determining that reaction starts.The catalyst used is 62.5wt.% FCC catalyst and 37.5wt.% ZSM-5 zeolite catalyst, the use of C/F charge ratios is 9.As a result it is shown in figure 12 and table 16.
Table 16
Model of the coke yield in 4wt.% to 6wt.% is respectively can be seen that from Figure 11 and 12 of embodiment 12 and 13 Enclose interior change.In large-scale conversion process such as FCC apparatus, the heat demand of conversion process is by producing in this process Heat caused by the burning of raw coke meets and by device thermal balance.It is burnt during converting according to the present invention The amount that charcoal is formed is enough to support to balance large-scale continuous recirculating fluidized bed riser-regenerator (riser- Regenerator) the heat required for operation, therefore caused coke is advantageously used to support thermal balance in this process.Can With by riser (riser) inject heavy substance (heavies) (undesirable product) or crackate and (produce other Alkene and coke) or weight product (fuel) is lighted in a regenerator without overcoming thermal balance using any other auxiliary fuel In any deficiency.
Embodiment 14
Tested with determination and catalyst mixture dividually by the influence for feeding addition reactor and with working as well The situation when charging of mixing is added together with catalyst compares.In the case of independent addition charging and catalyst, it will wrap The 6gm catalyst mixtures of spent FCC catalyst containing 75wt.% and 25wt.% ZSM-5 zeolite catalyst add reactor and Allow to stablize temperature of reactor.Under 620 DEG C of reaction temperature, the plastics incoming mixture that 1g has composition shown in table 3 is added Enter reactor and collect product.In the second experiment, the charging of the good mixing of amount same as described above and catalyst are added anti- Device is answered, wherein reaction temperature is initially 620 DEG C.Collect product.In two research, using 150Ncc/min fluidisation N2Gas Body flow.The result of this two researchs is shown in table 17 below.
Table 17
When mixing well and adding charging and catalyst, slightly higher conversion is realized, although conversion ratio is similar.From In table 17, it is clear that for effective utilization of catalyst, preferably charging and catalyst mixing is uniform.Therefore it is deeper Catalyst bed can not be provided with feeding sufficient mix.Therefore, charging and the good mixing of catalyst, preferred feedstock and catalysis The cocurrent mixing (co-current mixing) of agent can aid in charging preferably conversion.
It is apparent to those skilled in the art although describing the present invention in the form of it only by some , it is not restricted, but can carry out various change and change without departing from the scope of the present invention.Therefore, fit When understanding appended claims broadly and in a manner consistent with the scope of the invention.

Claims (19)

1. a kind of produce the method for alkene and aromatic compounds from raw material, methods described includes：
Contact plastic raw materials and carbon monoxide-olefin polymeric at 550 DEG C or higher of temperature, the carbon monoxide-olefin polymeric includes stream Fluidized catalytic cracking catalyst and ZSM-5 zeolite catalyst, the amount of wherein ZSM-5 zeolite catalyst account for the fluid catalytic cracking and urged The 10wt.% to 50wt.% of agent and the gross weight of the ZSM-5 zeolite catalyst, wherein the fluid catalytic cracking is catalyzed Agent and the ZSM-5 zeolite catalyst are different, and the catalyst of the raw material and carbon monoxide-olefin polymeric and the ratio of charging are 6 or more Greatly；And
Allow at least one that at least part of raw material is converted into alkene and aromatic compounds.
2. the method according to claim 11, wherein：
The fluidized catalytic cracking catalyst is made up of following at least one：X zeolites, Y zeolites, USY zeolite, modenite, eight Face zeolite, nano-crystalline zeolites, MCM mesopore materials, SBA-15, silicon-aluminate or phosphate, phosphoric acid gallium and titanium phosphate.
3. the method according to claim 11, wherein：
The fluidized catalytic cracking catalyst is made up of following at least one：Y zeolites and the USY zeolite being embedded in matrix, institute Stating fluidized catalytic cracking catalyst has 100m2/ g to 400m2/ g total surface area, the coke of by weight 0 to 0.5% amount Deposition.
4. the method according to claim 11, wherein：
The fluidized catalytic cracking catalyst is the non-fresh fluidisation with the coke laydown by weight more than 0 to 0.5% Catalytic cracking catalyst.
5. the method according to claim 11, wherein：
The fluidized catalytic cracking catalyst has 100m2/ g to 200m2/ g total surface area.
6. the method according to claim 11, wherein：
The amount of the ZSM-5 zeolite catalyst of the carbon monoxide-olefin polymeric accounts for the fluidized catalytic cracking catalyst and the ZSM-5 The 30wt.% of the gross weight of zeolite catalyst to 45wt.%.
7. the method according to claim 11, wherein：
The raw material and the carbon monoxide-olefin polymeric contact at a temperature of 570 DEG C to 730 DEG C.
8. the method according to claim 11, wherein：
The catalyst of the raw material and the carbon monoxide-olefin polymeric is 8 or bigger with the ratio fed.
9. the method according to claim 11, wherein：
The plastic raw materials include following at least one：Polyolefin, polystyrene, PET, polyvinyl chloride, Polyamide, makrolon, polyurethane, polyester, natural and synthetic rubber, tire, filled polymer, composite, plastic alloy, Plastics, biomass, bio oil and the oil of dissolving in a solvent.
10. the method according to claim 11, wherein：
The plastic raw materials and the carbon monoxide-olefin polymeric contact in the reactor, and the reactor is following at least one：Stream Fluidized bed reactor, bubbling bed reactor, slurry-phase reactor, reacting in rotary kiln device and packed bed reactor.
11. the method according to claim 11, wherein：
The fluidized catalytic cracking catalyst is the non-fresh fluidisation with by weight 0.2% to 0.5% coke laydown Catalytic cracking catalyst.
12. a kind of produce the method for alkene and aromatic compounds from raw material, methods described includes：
Contact plastic raw materials and carbon monoxide-olefin polymeric at 550 DEG C or higher of temperature, the carbon monoxide-olefin polymeric includes stream Fluidized catalytic cracking catalyst and ZSM-5 zeolite catalyst, the amount of wherein ZSM-5 zeolite catalyst account for the fluid catalytic cracking and urged The 10wt.% to 50wt.% of agent and the gross weight of the ZSM-5 zeolite catalyst, wherein the fluid catalytic cracking is catalyzed Agent is different with the ZSM-5 zeolite catalyst, and the fluidized catalytic cracking catalyst is that have to be more than 0 to 0.5% by weight Coke laydown and there is 100m2/ g to 400m2The non-fresh fluidized catalytic cracking catalyst of/g total surface area, it is described The catalyst of raw material and the carbon monoxide-olefin polymeric is 6 or bigger with the ratio fed；And
Allow at least one that at least part of raw material is converted into alkene and aromatic compounds.
13. the method according to claim 11, wherein：
The fluidized catalytic cracking catalyst is made up of following at least one：X zeolites, Y zeolites, USY zeolite, modenite, eight Face zeolite, nano-crystalline zeolites, MCM mesopore materials, SBA-15, silicon-aluminate or phosphate, phosphoric acid gallium and titanium phosphate.
14. the method according to claim 11, wherein：
The fluidized catalytic cracking catalyst is made up of following at least one：Y zeolites and the USY zeolite being embedded in matrix.
15. the method according to claim 11, wherein：
The fluidized catalytic cracking catalyst is the non-fresh fluidisation with by weight 0.2% to 0.5% coke laydown Catalytic cracking catalyst.
16. the method according to claim 11, wherein：
The fluidized catalytic cracking catalyst has 100m2/ g to 200m2/ g total surface area.
17. the method according to claim 11, wherein：
The amount of the ZSM-5 zeolite catalyst of the carbon monoxide-olefin polymeric accounts for the fluidized catalytic cracking catalyst and the ZSM-5 The 30wt.% of the gross weight of zeolite catalyst to 45wt.%.
18. the method according to claim 11, wherein：
The raw material is to include following at least one plastic raw materials：Polyolefin, polystyrene, PET, Polyvinyl chloride, polyamide, makrolon, polyurethane, polyester, natural and synthetic rubber, tire, filled polymer, composite, The plastics of plastic alloy and dissolving in a solvent.
19. a kind of produce the method for alkene and aromatic compounds from raw material, methods described includes：
Contact plastic raw materials and carbon monoxide-olefin polymeric at 550 DEG C or higher of temperature, the carbon monoxide-olefin polymeric includes stream Fluidized catalytic cracking catalyst and ZSM-5 zeolite catalyst, the amount of wherein ZSM-5 zeolite catalyst account for the fluid catalytic cracking and urged The 10wt.% to 50wt.% of agent and the gross weight of the ZSM-5 zeolite catalyst, wherein the fluid catalytic cracking is catalyzed Agent is different with the ZSM-5 zeolite catalyst, and the fluidized catalytic cracking catalyst is that have by weight 0.2% to 0.5% Coke laydown and there is 100m2/ g to 200m2The non-fresh fluidized catalytic cracking catalyst of/g total surface area, it is described The catalyst of raw material and the carbon monoxide-olefin polymeric is 6 or bigger with the ratio fed；And
Allow at least one that at least part of raw material is converted into alkene and aromatic compounds.
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